Ultrafine Au quantum clusters (QCs) were synthesized by etching host Au nanoparticles in the presence of ethylenediamine (en) and exhibited both strong photoluminescence (PL) and specific anticancer activity. The cutting-edge feature of this QC compound comprises subnanometer-size rhombohedral Au8, which consists of 8 units of the anticancer motif, namely, an Au+(en) complex (Au(en)QCs), which contributes to photo- and physicochemical stability as well as subcellular theranostic activity in intracellular PL imaging and in situ targeting. Moreover, the Au(en)QCs can be surface-encapsulated by transferrins (Tf) to create TfAu(en)QCs as a multipurpose drug carrier owing to numerous merits, which include cancer-selective biolabeling, high loading/release efficiency, high activity against drug-resistant tumor cells, low toxicity to normal cells, and physiological stability against biothiols, e.g., glutathiones. These versatile features, which are due to intrinsic optical and anticancer properties, provide potential as a single-drug delivery PL probe for preclinical applications, which has yet to be achieved using conventional nanoclusters.